JPS62175745A - Color image forming method - Google Patents

Abstract

PURPOSE:To obtain the excellent color image for a short period by processing a photographic sensitive material contg. a specific compd. according to a prescribed operation, substantially without using benzyl alcohol. CONSTITUTION:The titled method lies in developing the silver halide color photographic sensitive material which forms a photographic layer contg. the compd. shown by the formula on a reflective substrate with a color developer which does not substantially contain benzyl alcohol for <=2.5min, after exposing it. In the formula, R1 is an alkyl or an aromatic group, R2 is hydrogen atom, a bivalent linking group or an alkyl group, R3 and R4 are each hydrogen atom or an alkyl group, L1 is a bivalent linking agent, L2 and L3 are each a monova lent, a bivalent or a trivalent linking group, (n) is an integer of 1 or 2, A is a repeating unit obtd. by copolymerizing a monomer, X1 and X2 are each hydro gen atom or a cation, (x), (y) and (z) are each an added molar number, Q is a monovalent group. Thus, the preparation of a developer is simplified by using substantially no benzyl alcohol.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a color image forming method using a silver halide color light-sensitive material, and in particular to a color image forming method that does not use benzyl alcohol and has a shortened processing time. Regarding.

<Prior art> In order to form a color photographic image, three color photographic couplers of yellow, magenta and cyan are contained in a photosensitive layer, and after exposure, the layer is treated with a color developing solution containing a color developing agent. . In this process, the oxidized product of the aromatic primary amine reacts with the coupler to give a coloring dye, but in this case, it is important to give as high a color density as possible within the limited development time. is necessary.

To obtain high color density, use couplers with as high a coupling rate as possible, or couplers that are easily developed and
And development per unit coating amount! I! This is usually achieved by using a large amount of silver halide emulsion or by using a color developer with a high development rate.

Problems to be Solved by the Present Invention> In order to speed up the development of a silver halide emulsion, it is easy to think of increasing the silver chloride content of the silver halide, but as the silver chloride content increases, the sensitivity decreases. It has the disadvantage that it tends to deteriorate and cause fogging. Further, in order to increase the amount of developed silver, it is possible to increase the above-mentioned silver chloride content or to strengthen chemical sensitization, but this also has the disadvantage that fog is likely to occur. Reducing the grain size of the silver halide emulsion is also a means of speeding up development, but it has the fatal drawback of decreasing sensitivity. A method using a silver chloride emulsion is described, for example, in JP-A-58-953.
No. 45, No. 59-232342 and No. 60-191
No. 40, however, the fog is high and it is not suitable for practical use.

On the other hand, various measures have been conventionally taken regarding color developing solutions to speed up development. Among them, various additives have been studied in order to accelerate the penetration of the color developing agent into the color coupler-dispersed oil droplets and promote color development.In particular, a method of adding benzyl alcohol to the color developer to accelerate color development has been proposed. Because of its great color development promoting effect, it is currently widely used in the processing of color photographic materials, especially color papers.

However, when benzyl alcohol is used, diethylene glycol, triethylene glycol, alkanolamine, etc. are required as a solvent due to its low water solubility. However, since these compounds, including benzyl alcohol, have a high pollution load value, BODJPCOD, it is preferable to remove benzyl alcohol for the purpose of reducing the pollution load.

Furthermore, even if this solvent is used, it takes time to dissolve benzyl alcohol, so it is better not to use benzyl alcohol in order to reduce the preparation work.

Furthermore, if benzyl alcohol is brought into the bleaching bath or bleach-fixing bath, which is a post-bath, it causes the formation of a leuco dye, which is a cyan dye, and causes a decrease in color density. Furthermore, since the washing-out speed of the developer components is delayed, the image storage stability of the photosensitive material may be adversely affected.

Therefore, also for the above reasons, it is preferable not to use benzyl alcohol.

Conventionally, color development has generally been processed in 3 to 4 minutes, but with the recent shortening of finishing delivery times and the reduction of laboratory work, it has been desired to shorten the processing time.

However, if benzyl alcohol, which is a color development accelerator, is removed and the development time is shortened, it is inevitable that the color density will be significantly reduced.

In order to solve this problem, various color development accelerators (for example, U.S. Pat. No. 2,950,970, U.S. Pat. No. 2,515,1
No. 47, No. 2,496,903, No. 2,304,92
No. 5, No. 4,038.075, No. 4,119,462
British Patent No. 1,430°998, British Patent No. 1,455,4
No. 13, JP-A-53-15831, JP-A No. 55-6245
No. 0, No. 55-62451, No. 55-62452,
Even when used in combination with the compounds described in Japanese Patent Publication No. 55-62453, Japanese Patent Publication No. 51-12422, and Japanese Patent Publication No. 55-49728, sufficient color density could not be obtained.

Methods of incorporating 3-pyrazolidones (e.g., JP-A-60
No. -26338, No. 60-158444, No. 60-1
Even if the method described in No. 58446 is used, there are disadvantages in that the sensitivity decreases at the time of the main peak and fog occurs.

Also, a method of incorporating a color developing agent (for example, U.S. Pat. No. 37
No. 19492, No. 3342559, No. 3342597
No., JP-A-56-6235, JP-A No. 56-16133,
Even if the method described in Japanese Patent No. 57-97531, Japanese Patent No. 57-83565, etc. is used, it is not an appropriate method because it has drawbacks such as slow color development and generation of capri.

As described above, no method has been found for obtaining sufficient color images in a short time using a color developing solution that does not substantially contain benzyl alcohol.

(Means to solve the problem) The object of the invention was achieved by the method described below.

After exposure, a silver halide color photographic light-sensitive material having a photographic layer containing a compound represented by the general formula (I) provided on a reflective support was developed for 2 minutes and 30 minutes in a color developer substantially free of benzyl alcohol. A color image forming method characterized by developing in less than a second.

General formula (I) [wherein R1 represents a substituted or unsubstituted alkyl group or aromatic group, R2 is a hydrogen atom or -C-L, -R
3 (here, R4 represents a divalent linking group, ^ R2 represents a hydrogen atom or a substituted or unsubstituted alkyl or aromatic group), and R3 and R4 independently represent a hydrogen atom or a substituted or unsubstituted alkyl or aromatic group. represents an alkyl group.

Ll represents a divalent linking group, and Ll and L:l each independently represent a single bond or a divalent or trivalent linking group. n represents an integer of 1 or 2.

A represents a repeating unit copolymerized with an ethylenically unsaturated monomer copolymerizable with the monomer providing the y component and the two components. Xl and X2 each independently represent a hydrogen atom or cation, and x, y, and 2 each represent a value indicating the average number of moles added of each monomer. Q represents a monovalent group. ] Here, "containing substantially no benzyl alcohol" means that the concentration of benzyl alcohol in the developer is 0.
．． It means 5 ml/l or less. Preferably, the developer does not contain benzyl alcohol.

i) A compound represented by general formula (I) used in the present invention.

The compound represented by general formula (I) used in the present invention is:
It is a surface active polymer useful as an emulsifier and dispersant.

Preferred compounds for use in the present invention are of the general formula (I)
in which R1 is a substituted or unsubstituted alkyl group having 8 to 24 carbon atoms, or a general formula [wherein R, and R1
is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, or a C 1 to 10
represents an alkoxy group, and R6 and R2 may be the same or different. Ra is a hydrogen atom or R1 independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 6 to 18 carbon atoms, or R1 and RIo together form a nitrogen-containing ring) It is a compound like this.

Particularly preferred compounds for use in the present invention are substituents R
1 is an alkyl group having 8 to 12 carbon atoms whose raw materials are easily available;
2 alkyl group), R11'' \- (here R1
□,
/C0NHR+a 8-18 alkyl group), etc.

and represents a divalent linking group, -5-1-8○2- or -CR,5OH- (where RIS is H5 having 1 to 12 carbon atoms)
(alkyl group) is particularly preferred.

A is a repeating unit formed by copolymerizing an ethylenically unsaturated monomer copolymerizable with the y-component and the 7-mer that provides the 2-component, such as ethylene, propylene, 1-butene,
alkylene such as isobutyne, styrene, α-methylstyrene, vinyltoluene, ethylenically unsaturated esters of aliphatic acids (e.g. vinyl acetate, allyl acetate), monocarboxylic esters of ethylenically unsaturated monomers or dicarboxylic acids. Esters (e.g. methyl methacrylate, ethyl acrylate, n-butyl acrylate,
n-butyl methacrylate, n-octyl acrylate, benzyl acrylate), substituted monoethylenically unsaturated compounds (e.g. acrylonitrile), or dienes (e.g. butadiene, isoprene), etc.
Among these, acrylonitrile, styrene, vinyl acetate,
Methyl acrylate, methyl methacrylate, n-butyl acrylate, n-octyl acrylate, etc.
Particularly preferred. A may contain two or more of the above monomer units.

It is a repeating unit obtained by copolymerizing an ethylenically unsaturated monomer copolymerizable with a monomer that provides two components, and may contain two or more types of seven-unit units.

In the present invention, R2 is a hydrogen atom or) NH, Rs
R2 is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and particularly preferred is a compound in which R2 is a hydrogen atom or -C-OH or the like.

R3 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, particularly preferably a hydrogen atom or a methyl group.

Lt represents a single bond, divalent or trivalent linking group,
Among these, a divalent linking group represented by a single bond or the like is preferred. In the above formula, R4 represents a hydrogen atom or an alkyl group, and R17 represents alkylene, arylene, or aralkylene. m is 0,
Represents an integer of either ■ or 2.

Among these, L2 is a single bond, etc. are particularly preferred.

Xl represents a hydrogen atom or a cation, especially a hydrogen atom,
Sodium and potassium are preferred.

n is preferably 1.

R.

It is a repeating unit obtained by copolymerizing an ethylenically unsaturated monomer copolymerizable with a monomer providing the component y, and may contain one unit of two or more types of monomers.

R4 represents a hydrogen atom or a substituted or unsubstituted alkyl group, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and particularly preferably a hydrogen atom or a methyl group.

L represents a single bond, a divalent or trivalent linking group, and especially a single bond or \-0me\. □2ゎ, ＼, -1〆. Hz OR+a, preferred. In the above formula, R+s and RI9 represent the same or different alkylene, arylene, aralkylene, m
represents an integer of O, l, or 2. Among these, L is a single bond, CH.

etc. are particularly preferred.

X2 represents a hydrogen atom or a cation, especially a hydrogen atom,
Sodium and potassium are preferred. n is preferably 1.

x, y and 2 are values indicating the average number of added moles of each monomer, and are preferably from 0 to 50, particularly when X is O
~15, (y+2) is preferably 1 to 15,
The sum of x, y and 2 is preferably 40 or less. Q represents a hydrogen atom, an initiator residue, a chain transfer agent residue, etc.

The compound of formula (j) is generally a random copolymer, but may also be a block copolymer.

The molecular weight of the compound of general formula (I) used in the present invention is not particularly limited, but is preferably about 280 to about 10
．． 000, particularly preferably about 300 to about 5,00
It is 0.

General formula N that can be preferably used in the present invention
) Specific examples of compounds represented by x,
As described above, y and 2 each indicate the average number of moles added of each monomer, but the values of x, y, and 2 are not limited to the following combinations. ).

Cq H+q CH(CH3)Z (8) O +1 CH.

■ C1□Hzs S +CHz CH toreko HO
OH Hibiki□・C+Ji* S+CHz-COh7 ``HSo, Na (28) ・=・ (29) CH2 c) I3 CIIIC Hit H ■ IJLan 啼 (35) CH to SO8.

Shiku JNtlC-CHtSIJzh C.I.

(36)　　　　　co.

01□H2S5-+ C11ZCSE "-11 CH,
CH 斤τ「1coocH、C0NH ME＼ (37)
c) l:1OHC00CHxC
00II These compounds represented by the general formula (I) of the present invention can be prepared by combining one or more types of X in the presence of a chain transfer agent.
It is synthesized by radical polymerization of an ethylenically unsaturated monomer mixture consisting of at least one of component and component y or two components. Regarding chain transfer agents, please refer to the bottom of the page, for example, Takayuki Otsu Lecture on Polymerization Reaction Theory 1 "Radical Polymerization (I)" Kagaku Dojin (I
971) can be used. In addition, radical polymerization can be carried out by a method described in "Experimental Methods of Polymer Synthesis" by Masayoshi Kinoshita and Tsuyoshi Otsu, Kagaku Dojin (I972).

More specifically, U.S. Patent No. 3,668,230, U.S. Pat. It can be synthesized according to the method described in Vol. 341 (I976). Although alkyl mercaptans are used as telogens in the above five patent documents, it is well known to those skilled in the art of organic synthesis that other aliphatic mercapto compounds and aromatic mercapto compounds can be used in the same way. .

ii) Surfactants that can be used in combination The compound of general formula (I,) used in the present invention can be used not only alone, but also in combination with other non-polymer surfactants. In some cases, it may be preferable to use the surfactant in combination with a low-molecular-weight surfactant rather than using it alone. The compound of general formula (I) used in the present invention can be used in combination with a so-called anionic surfactant and/or a nonionic surfactant.

The anionic surfactant has a hydrophobic group having 8 to 30 carbon atoms in one molecule and -303M or -03
It is preferable to use a compound having both 0 and M groups (M has the same meaning as in the general formulas Cl-1 and Cl-2). This type of compound has been described by Ryohei Oda,
"Synthesis and Applications of Surfactants" by Kou (Maki Shoten Edition) and "Surface Active Agents" by Berry (
A. W. Perry, “5 surface Active.
Agents” (Interscience Public-cat
ions Inc., New York)).

As the above-mentioned nonionic surfactant, JP-A-48-30
It is preferable to use a nonionic surfactant and a polyhydric alcohol fatty acid ester surfactant described in No. 933. The polyhydric alcohol fatty acid ester surfactant preferably has at least two, preferably at least three, hydroxyl groups, and preferably has 6 to 25 fatty acid carbon atoms. Specifically, sorbitan fatty acid ester nonionic surfactants described in US Pat. No. 3,676,141 are advantageously used in the present invention.

Specific examples of the anionic surfactant include the following compounds.

(A 1) C+zHzsO3O*Na(A
2) C+aHzqOS O:l Na(A-3
) Funnel oil (A-4) C+zHzsCONHN a 03
SOCH2CH2 (A 5) C+4HzqSOx Na(A
6) C+4HzqSOx Na (A-7)
0CHzCHzOCHzCHzSO: +Na/ ~ +1 1 °\, Cs H+ -1 (A 8) Na0zSCH-C00CsH+t
C) (z・C00CsHl? (A-9) So, Na / ~ I282S (A-10) So, Na NHOCCI3H2? (A-11) 03Na In the present invention, the compound of general formula (I) used in the present invention An anion having at least one hydrophobic group having 8 to 30 carbon atoms and a -8O!M or -SO□M group (M has the same meaning as in (I) above) in one molecule. It is particularly preferable to use at least one surfactant and/or at least one fatty acid ester nonionic surfactant of sorbitan in combination.

In the present invention, the coupler must be heated and melted or dissolved in an organic solvent to make it liquid before the emulsification operation. Compounds that can be directly emulsified by melting are limited to compounds with a melting point of about 90°C or less.

As the organic solvent (ie, so-called oil) used to finely disperse the coupler in the aqueous medium, it is useful to use one that is virtually insoluble in water and has a boiling point of 190° C. or higher at normal pressure. Organic solvents of this type can be selected from carboxylic esters, phosphoric esters, carboxylic amides, ethers, and substituted hydrocarbons. Specific examples include di-n-butyl fucuric acid ester, di-isooctylfural ester, dimethoxyethyl phthalic ester, di-n-butyl adipate, diisooctyl azelenate, tri- n-butyl phthalate, butyl laurate, di-n-sebacate, tricresyl phosphate, tri-n-butyl phosphate, triisooctyl phosphate, N・N-diethylcaprylic acid amide, N-
N-dimethylpalmitic acid amide, n-butyl-m-pentadecyl phenyl ether, ethyl-2.4-ter
Examples include t-butylphenyl ether and chlorinated paraffin.

In the present invention, in addition to such a solvent, it is advantageous to use a low boiling point solvent (one with a boiling point of 130° C. or less at room pressure) or a water-soluble high boiling point solvent in order to dissolve the coupler. Sometimes. For example, propylene carbonate,
Ethyl acetate, butyl acetate, ethyl propionate, sec -7'+ alcohol, tetrahydrofuran, cyclohexitane, dimethylformamide, diethyl sulfoxide, methyl cellosolve, etc.

As the emulsification device used to carry out the present invention, one that applies a large shearing force to the processing liquid or one that applies high-intensity ultrasonic energy is suitable. Particularly, emulsifying devices having a colloid mill, a homogenizer, a capillary emulsifying device, a liquid siren, a 'tfet strain type ultrasonic generator, and a Pohlmann whistle can give good results.

The photographic layer containing the compound of general formula (I) used in the present invention is preferably a silver halide emulsion layer and/or a layer adjacent thereto, and particularly preferably a silver halide emulsion layer.

The amount of the compound of general formula (I) used in the present invention depends on the type of coupler used, the type of other additives coexisting, the type and amount of the dispersion solvent, and, in some cases, other surfactants used in combination. It varies depending on the type and amount, etc., but in general, it is a dispersion! (ie, a solution of couplers and other oil-soluble photographic additives dissolved in a dispersion solvent) is preferably 0.2 to 50% by weight.

As substances that coexist with the coupler, oil-soluble photographic additives such as anti-fading agents, ultraviolet absorbers, DIR couplers, and antioxidants can be included.

The "reflective support" used in the present invention is one that enhances the reflectivity and makes the dye image formed in the silver halide emulsion layer clearer. Examples include those coated with a hydrophobic resin containing a dispersed light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate, and those using a hydrophobic resin containing a dispersed light-reflecting substance as a support. For example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with a reflective layer or a reflective material, such as glass plates, polyester films such as polyethylene terephthalate, cellulose triacetate or cellulose nitrate, polyamide There are films, polycarbonate films, polystyrene films, etc., and these supports can be appropriately selected depending on the purpose of use.

Next, a processing step (image forming step) in the present invention will be described.

The color development processing step in the present invention has a short processing time of 2 minutes and 30 seconds or less. The preferred treatment time is 1 to 2 minutes. The processing time herein refers to the time from the time when the photosensitive material comes into contact with the color developer until it comes into contact with the next bath, and includes the time during which the photosensitive material is transferred from one place to another.

The color developing solution used in the development process of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As this color developing agent, p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline, and 3-methyl-4-amino-N-ethyl-N.
-β-hydroxylethylaniline, 3-methyl-4-
Amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-
N-β-methoxyethylaniline and their sulfates, hydrochlorides, phosphates or p-toluenesulfonates, tetraphenylborate Lp-(t-octyl)benzenesulfonates, and the like.

Examples of aminophenol derivatives include 〇-aminophenol, p-aminophenol, 4-amino-2-
These include methylphenol, 2-amino-3-methylphenol, 2-oxy-3-amino-1,4-dimethylbenzene, and the like.

In addition, "Photographic Processing Chemistry" by F. A. Meson, Focal Press (
I966) (L, F, A.

Mason, “Photographic Processes
sing Chemistry”.

Focal Press), pages 226-229, U.S. Pat. No. 2,193,015, U.S. Pat.
Those described in JP-A No. 48-64933 may also be used. If necessary, two or more color developing agents may be used in combination.

The processing temperature of the color developer in the present invention is 30°C to 5°C.
The temperature is preferably 0°C, more preferably 33°C to 45°C.

Further, as the development accelerator, various compounds may be used, except that they do not substantially contain benzyl alcohol. For example, U.S. Patent No. 2,648,604, Japanese Patent Publication No. 44-95
03, U.S. Patent No. 3,171.247, various pyrimidylam compounds and other cationic compounds, cationic dyes such as phenosafranin, neutral salts such as thallium nitrate and potassium nitrate, and Japanese Patent Publication No. 1986-930.
No. 4, U.S. Patent No. 2,533,990, U.S. Patent No. 2,531.
No. 832, No. 2,950,970, No. 2゜577.1
Nonionic compounds such as polyethylene glycol and its derivatives and polythioethers described in No. 27, US Patent No. 3
Examples include the 1,000-onythyl compounds described in JP-A-58-156934 and JP-A-60-220344.

In addition, in short-time development processing as in the present invention,
An important issue is not only a means to accelerate development, but also a technique to prevent development fog. Preferred antifoggants in the present invention include alkali metal halides such as potassium bromide, sodium bromide, and potassium iodide, and organic antifoggants.

Examples of organic antifoggants include benzotriazole, 6-nidropenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, Nitrogen-containing heterocyclic compounds such as 2-thiazolylmethyl-benzimidazole, hydroxyazaindolizine, and 1-phenyl-
Mercapto-substituted heterocyclic compounds such as 5-mercaptotetrazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, as well as mercapto-substituted aromatic compounds such as thiosalicylic acid can be used. Particularly preferred are halides. These antifoggants may be eluted from the color photosensitive material during processing and may accumulate in the color developer.

In addition, the color developer according to the present invention includes a pH buffering agent such as an alkali metal carbonate, borate or phosphate; hydroxylamine, triethanolamine, a compound described in OLS No. 2622950; , preservatives such as sulfites or bisulfites; organic solvents such as diethylene glycol; dye-forming couplers; competitive couplers; nucleating agents such as sodium boron hydride; auxiliary development such as 1-phenyl-3-pyrazolidone. Drugs; viscosity imparting agents; ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, N-hydroxymethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, and those described in JP-A-58-195845 Examples of compounds such as aminopolycarboxylic acid and 1-hydroxyethylidene-1,1'-diphosphonic acid, Research Disclosure
aminotris (methylene phosphonic acid), an organic phosphonic acid described in 18170 (May 1979),
Aminophosphonic acids such as ethylenediamine-N, N, N", N"-tetramethylenephosphonic acid, JP-A-52-102726, JP-A-53-42730, JP-A-5
No. 4-121127, No. 55-4024, No. 55-4
No. 025, No. 55-126241, No. 55-659
No. 55, No. 55-65956, and Research Disclosure.
ure) ml No. 8170 (May 1979), chelating agents such as phosphonocarboxylic acids can be contained.

In addition, the color developing bath can be divided into two or more parts as necessary.
Replenish color developer replenisher from the first bath or last bath,
The development time may be shortened or the amount of replenishment may be reduced.

After color development, the silver halide color photosensitive material is usually bleached. The bleaching treatment may be carried out simultaneously with the fixing treatment (bleaching and fixing) or may be carried out separately. Examples of bleaching agents include compounds of polyvalent metals such as iron ([[), cobalt (■), chromium (■), copper (n)], peracids,
Quinones, nitroso compounds, etc. are used. For example, ferricyanide, dichromate, iron ([[) or cobal) (m)(D Jan salts, such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propatol Complex salts of aminopolycarboxylic acids such as tetraacetic acid or organic acids such as citric acid, tartaric acid, malic acid; persulfates, manganates;
Nitrosophenol and the like can be used. Among these, potassium ferricyanide, iron ethylenediaminetetraacetate (sodium I[[) and iron ethylenediaminetetraacetate (
Particularly useful are I[[] ammonium, triethylenetetraminepentaacetate iron (I[I) ammonium, persulfate salts. The ethylenediaminetetraacetic acid iron (I[[) complex salt is active both in stand-alone bleach solutions and in -bath bleach-fix solutions.

Further, various accelerators may be used in combination with the bleaching solution and the bleach-fixing solution, if necessary. For example, in addition to bromide ion and iodide ion, U.S. Pat.
No. 6, No. 49-26586, JP-A-53-32735
Thiourea-based compounds as shown in JP-A No. 53-36233 and JP-A No. 53-37016;
No. 3-57831, No. 53-32736, No. 53-6
No. 5732, No. 54-52534 and U.S. Patent No. 3,
Thiol-based compounds as shown in 893,858, etc., or JP-A-49-59644 and JP-A-50-
No. 140129, No. 53-28426, No. 53-14
No. 1623, No. 53-104232, No. 54-357
Heterocyclic compounds described in JP-A No. 27, etc.; thioether compounds described in JP-A-52-20832, JP-A-55-25064, and JP-A-55-26506; Compounds such as quaternary amines described in JP-A-48-84440 or thiocarbamoyls described in JP-A-49-42349 may also be used.

Examples of the fixing agent include thiosulfates, thiocyanates, 1,000-onythyl compounds, thioureas, and a large amount of iodides, but thiosulfates are generally used. As the preservative for the bleach-fix solution and the fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

After the bleach-fixing process and the fixing process, a washing process is usually performed. In the water washing process, various known compounds may be added for the purpose of preventing precipitation and saving water. For example, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphoric acid to prevent precipitation, disinfectants and anti-bacteria to prevent the growth of various bacteria, algae, and mold, magnesium salts, and aluminum salts. Typical hardeners, surfactants for preventing drying load and unevenness, etc. can be added as necessary. Or L.E. West (L,
E, West), Photographic Science and Engineering (Photo.

Sci, and Eng,), Volume 9, No. 6, (I
965) and the like may be added.

In particular, the addition of chelating agents and anti-piping agents is effective.

It is also possible to save water by using a multistage (for example, 2 to 5 stages) countercurrent method in the water washing process.

Also, after or instead of the water washing process, JP-A-57-
A multi-stage countercurrent stabilization treatment process such as that described in No. 8543 may be performed. In the case of this step, a countercurrent column with 2 to 9 tanks is required. Various compounds are added to this stabilizing bath for the purpose of stabilizing the image.

For example, buffers for adjusting membrane pH (e.g., borates, metaborates, borax, phosphates, carbonates, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acids, dicarboxylic acids, Polycarboxylic acids, etc.) and formalin can be given. In addition, water softeners (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), disinfectants (proxel, isothiazolone, 4-thiazolylbenzimidazole, halogenated phenol benzotriazoles, etc.), a surfactant, a fluorescent brightener, a hardening agent, etc. may be added.

Furthermore, various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate can be added as membrane pH adjusting agents after treatment.

The color coupler incorporated in the light-sensitive material is preferably diffusion-resistant by having a ballast group or being polymerized. A two-equivalent color coupler in which the coupling active position is substituted with a leaving group can reduce the amount of silver coated than a daily equivalent color coupler in which the coupling active position is a hydrogen atom. Couplers in which the color-forming dye has adequate diffusivity, non-color-forming couplers, or DIR couplers that release a development inhibitor or couplers that release a development accelerator upon coupling reaction can also be used.

A representative example of the yellow coupler that can be used in the present invention is an oil-protected acylacetamide coupler. A specific example is U.S. Patent No. 2.40
7.210, 2.875.057 and 3
．． The use of two-equivalent yellow couplers is preferred in the present invention, as described in U.S. Pat. No. 3,408,194, U.S. Pat.
No. 3,933,501 and No. 4,022゜62
0, etc., or Japanese Patent Publication No. 58-10739, U.S. Patent No. 4,
No. 401,752, No. 4,326.024, RD1
8053 (April 1979), British Patent No. 1.425
．． 020, West German Application No. 2.219.917, West German Application No. 2. 261. No. 361, same No. 2.329.587
Typical examples thereof include the nitrogen atom separation type yellow couplers described in No. 1, No. 2, 433.812, and the like. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness;
- Benzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include oil-protected indacylon or cyanoacetyl couplers, preferably pyrazoloazole couplers such as 5-pyrazolone and pyrazolotriazoles. The 5-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye. Same No. 2゜3
No. 43.703, No. 2,600.788, No. 2.
No. 908,573, same No. 3. 062. No. 653, No. 3,152,896 and No. 3936.015
It is written in the number etc. As a leaving group for a two-equivalent 5-pyrazolone coupler, U.S. Pat.
No. 4.3 or U.S. Patent No. 4.3.
The arylthio group described in No. 51,897 is preferred. Further, the 5-pyrazolone coupler having a ballast group described in European Patent No. 73.636 provides a high color density.

As a pyrazoloazole coupler, U.S. Patent No. 3,
Pyrazolobenzimidazoles as described in US Patent No. 369,879, preferably pyrazolo(5,1-c)(I,2,4) triazoles as described in US Pat.
(June 1984) and Research Disclosure 24230 (I9
Examples include the pyrazolopyrazoles described in June 1984). Imidazo(
I,2-b) pyrazoles are preferred, as described in European Patent No. 11
Pyrazolo [1°5-b3 (I
, 2,43 triazoles are particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenolic couplers, such as the naphthol-based couplers described in U.S. Pat. No. 2,474°293, and preferably U.S. Pat.
, No. 212, No. 4゜146.396, No. 4.22
Typical examples include two-equivalent naphthol couplers of the oxygen atom elimination type described in No. 8,233 and No. 4.296.200. Further, specific examples of phenolic couplers are given in U.S. Patent Nos. 2,369,929 and 2,
, No. 801,171, No. 2,772°162, No. 2,895.826, etc. Cyan couplers that are robust to humidity and temperature are preferably used in the present invention and are typically described in U.S. Pat.
72.002, a phenolic cyan coupler having an alkyl group greater than or equal to an ethyl group at the meta-position of the phenol nucleus, U.S. Pat. No. 2,772.162, U.S. Pat.
No. 758.308, same No. 4. 126. No. 396, No. 4,334.011, No. 4,327.173,
West German Patent Publication No. 3. 329. 729 and Japanese Patent Application No. 58-42671, etc., and U.S. Pat.
No. 446.622, No. 4.333,999, No. 4
．． 451. No. 559 and No. 4,427,767
Examples include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, as described in No.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such dye-diffusive couplers are described in U.S. Pat. Specific examples of magenta couplers are given in No. 366.237 and British Patent No. 2,125.570, and examples of yellow, magenta or cyan couplers are given in European Patent No. 96.570 and German Published Application No. 3,234.533. Specific examples are described.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. A typical example of a polymerized dye-forming coupler is U.S. Pat. No. 3,415,82.
No. 0 and No. 4,080°211. Specific examples of polymerized magenta couplers are described in British Patent No. 2. 102. No. 173 and U.S. Patent No. 4.367
．． It is described in No. 282.

The various couplers used in the present invention can be used in combination with two types of couplers in the same photosensitive layer, or in two different layers with the same compound, in order to satisfy the characteristics required for the photosensitive material. It is also possible to introduce more than one.

Typical usage amounts for color couplers range from 0.001 to 1 mole per mole of photosensitive silver halide, preferably from 0.01 to 0.1 mole for yellow couplers.
5 mole, 0°003 to 0.3 for magenta coupler
moles, and for cyan couplers 0, OQ2 to 0.3
It is a mole.

The light-sensitive materials produced using the present invention contain hydroquinone derivatives, aminophenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, and sulfonamide phenols as color-fogging inhibitors or color-mixing inhibitors. It may also contain derivatives and the like.

Known anti-fading agents can be used in the light-sensitive material of the present invention. Organic anti-fading agents include hydroquinones,
Hindered phenols, mainly 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols, and bisphenols;
Typical examples include gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and ethers or esters 3z3 bodies obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. Further, metal complexes such as (bissalicylaldoximado)nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel complex can also be used.

To prevent yellow dye images from deteriorating due to heat, humidity and light.
As described in U.S. Pat. No. 4,268,593,
Compounds having a hindered amine and a hindered phenol structure in the same molecule give good results. In addition, in order to prevent deterioration of the agenta dye image, especially deterioration caused by light, the substitution of spiroindanes described in JP-A-56-159644 and hydroquinone diether or monoether as described in JP-A-55-89835 is recommended. chromans give favorable results.

In order to improve the storage stability of cyan images, especially the light fastness, it is preferable to use a benzotriazole ultraviolet absorber in combination. This UV absorber may be co-emulsified with the cyan coupler.

The amount of ultraviolet absorber applied may be sufficient to impart photostability to the cyan dye image, but if too much is used, it may cause yellowing of the unexposed areas (white areas) of the color photographic window light material. Since there are
It is set in the range of mol/d to 1.5×10-gomol/d.

In the conventional light-sensitive material layer structure of color paper, an ultraviolet absorber is contained in one of the layers on both sides adjacent to the cyan coupler-containing red-sensitive emulsion layer, preferably in both layers. When an ultraviolet absorber is added to the intermediate layer between the green sensitive layer and the red sensitive layer, it may be co-emulsified with a color mixing inhibitor. When a UV absorber is added to the protective layer, another protective layer may be applied as the outermost layer. This protective layer can contain a matting agent of any particle size.

In the photosensitive material of the present invention, an ultraviolet absorber can be added to the hydrophilic colloid layer.

The light-sensitive material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation or halation.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the invention may contain a stilbene-based, triazine-based, oxazole-based, or coumarin-based brightener.

Water-soluble brighteners may be used, and water-insoluble brighteners may be used in the form of dispersions.

The present invention, as described above, is applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support.

Multilayer natural color photographic materials usually have a red-sensitive emulsion layer on a support,
Each of the green-sensitive emulsion layer and the pre-malignant emulsion layer has a small number (each has one. The order of these layers can be arbitrarily selected as necessary. Also, each of the earlier emulsion layers is composed of two or more emulsion layers having different sensitivities. Alternatively, a non-photosensitive layer may be present between two or more emulsion layers having the same malignancy.

The light-sensitive material according to the present invention includes, in addition to the silver halide emulsion layer,
Protective layer, intermediate layer, filter layer, halation,
It is preferable to provide auxiliary layers such as city layer and back calendar as appropriate.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein;
Cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfate esters, W derivatives such as sodium alginate, starch derivatives;
Various synthetic hydrophilic polymeric substances such as single or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be used.

Gelatin includes lime-processed gelatin, acid-processed gelatin, Bull, Soc, and Sci.

Phot, Japan, N [Li2.30 pages (I966
Enzyme-treated gelatin as described in ) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used.

In addition to the above-mentioned additives, the photosensitive material of the present invention further contains various stabilizers, anti-staining agents, developers or their precursors,
Development accelerators or precursors thereof, lubricants, mordants, matting agents, antistatic agents, plasticizers, and other various additives useful for photographic materials may be added. Representative examples of these additives are Research Disclosure 1764
3 (December 1978) and 18716 (I
(November 979).

The silver halide emulsion used in the present invention is silver bromide, silver chlorobromide, or silver chloride that does not substantially contain silver iodide, and the silver halide preferably used contains 2 to 80 mol% of silver chloride. Contains silver chlorobromide.

The silver halide grains used in the present invention may have different phases inside and on the surface, may have a multiphase structure such as a bonded structure, or may consist of a uniform phase throughout the grain. Moreover, they may be mixed.

Average grain size of silver halide grains used in the present invention (
In the case of spherical or near-spherical particles, the particle diameter is the particle size, and in the case of cubic particles, the principal is the particle size. Based on the projected area (gravel on average), it is preferably 2μ or less and 0.1μ or more, Particularly preferred is 0.15 μ or less of 1 μ
That's all. The grain size distribution may be narrow or wide, but the value (variation rate) obtained by dividing the standard deviation value of the grain size distribution curve of the silver halide emulsion by the average grain size is 20.
It is preferred to use so-called monodispersed silver halide emulsions within 15%, particularly preferably within 15%. In addition, in order to satisfy the target gradation of the coloring material, two or more types of monodisperse silver halide emulsions with different grain sizes are used in the opalescent layer having substantially the same coloring property (the monodispersity is defined as ) can be mixed in the same layer or coated in separate layers. Furthermore, two or more types of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or layered for use.

The shape of the silver halide grains used in the present invention is regular (cubic, octahedral, dodecahedral, dodecahedral, etc.).
), may have an irregular crystal shape such as a spherical shape, or may have a composite shape of these crystal shapes. Further, tabular grains may be used, and in particular, an emulsion may be used in which tabular grains having a length/thickness ratio of 5 or more, particularly 8 or more occupy 50% or more of the total projected area of the grains.

An emulsion consisting of a mixture of these various crystal forms may also be used. These various emulsions may be either a surface latent image type in which a latent image is mainly formed on the surface, or an internal latent image type in which a latent image is formed inside the grains.

The photographic emulsion used in the present invention is manufactured by Glafkides [Chemistry and Physics of Photography J (P., Glafkides).

Chimie et PhysiquePhoto
graphique (published by Pau1Mante1, 1
967)], Duffin, “Photographic Emulsion Chemistry J (G.
Photographic by F, Duf f in
Emulsion Chemistry (Focal
Press, 1966], Zelikman et al., "Manufacture and Coating of Photographic Emulsions J"
Making and Coati by eta1
ngPhotographic Emulsion (
Focal Press, 1964)]. That is, any of the acid method, neutral method, ammonia method, etc. may be used.
Further, as a method for reacting the soluble silver salt and the soluble halogen salt, any one of a one-sided mixing method, a simultaneous mixing method, a combination thereof, etc. may be used. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). As one form of the simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Furthermore, emulsions prepared by the so-called conversion method, which involves converting silver halide already formed into silver halide with a smaller solubility product before the completion of the silver halide grain formation process, and silver halide Emulsions which have undergone similar halogen exchange after the completion of the grain formation process can also be used.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present.

After grain formation, silver halide emulsions are usually subjected to physical ripening, desalting and chemical ripening before being used for coating.

Known silver halide solvents (for example, ammonia, Rodankali or U.S. Pat. No. 3,271,157, JP-A-5
1-12360, JP-A-53-82408, JP-A-53-144319, JP-A-54-10Q717 or JP-A-54-155828, etc.) by precipitation, It can be used for physical ripening and chemical ripening. In order to remove soluble root salts from the emulsion after physical ripening, washing with water, flocculation sedimentation, ultrafiltration, etc. are performed.

The silver halide emulsion used in the present invention contains active gelatin and sulfur-containing compounds that can react with silver (for example, thiosulfate,
Sulfur amplification method using reducing substances (e.g. stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds); metal compounds (For example, in addition to gold complex salts, Pt, Ir, Pd, Rh, F
A noble metal aggravation method using complex salts of metals of group 1 of the periodic table such as e) can be used alone or in combination.

Among the above chemical sensitizations, sulfur sensitization alone is more preferred.

The blue-sensitive, green-sensitive and red-sensitive emulsions of the present invention are each spectrally sensitized with a methine dye or the like so as to have color sensitivity. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes,
Included are styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.

Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. Namely, viroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these Nuclei fused with aromatic hydrocarbon rings to the nucleus of Nuclei, quinoline nuclei, etc. can be applied. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbyl nucleus, and the like can be applied.

These sensitizing dyes may be used alone or in combination, and combinations of enhancing dyes are often used particularly for the purpose of supersensitization. A typical example is US Patent 2
, No. 688,545, No. 2゜977.229, No. 3,
397.060, 3.522,052, 3.5
No. 27,641, No. 3,617,293, No. 3,62
No. 8,964, No. 3,666.480, No. 3. 67
2. No. 898, No. 3,679,428, No. 3,70
3゜377, 3,769,301, 3,814
．． No. 609, No. 3,837,862, No. 4°026.
707, British Patent No. 1,344,281, British Patent No. 1,50
No. 7,803, Special Publication No. 43-4936, No. 53-12
No. 375, JP-A-52-110618, JP-A No. 52-10
No. 9925.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion.

(Examples) The present invention will be explained in detail below using Examples, but the present invention is not limited thereto.

Example ■.

3 ethyl acetate to 24.0 g of yellow coupler (Y-1)
5rrl and as solvent, diptyl phthalate l'1m
160 mj of a 12% aqueous gelatin solution containing 1 Qml of a 10% solution of the comparative compound R-1 (sodium dibutylnaphthalene sulfonate) shown below, using this solution as an emulsifying dispersant. and emulsified and dispersed using a high-speed stirrer.

The entire amount of this emulsified dispersion was added to a silver chlorobromide emulsion (containing 70 g/kg of Ag) consisting of 80% Br, and the silver coating amount was 0.3
A comparative sample (A) was prepared by coating the sample on a paper support laminated with polyethylene on both sides at a concentration of 1 g/m'', and providing a gelatin layer on top of this coated layer.

Next, samples (B) to (R) were prepared as follows.

- The same sample as sample (A) except that 1.0 g of the exemplary compound (I) of the present invention was used as an emulsifying dispersant instead of R-1. The same sample as sample (A) except that 1.0 g of the exemplary compound (5) of the present invention was used instead of R-1.The exemplary compound of the present invention was used instead of R-1 as an emulsifying dispersant. Same sample as sample (A) except that 1.0 g of (I1) was used. Except that 1.0 g of the exemplary compound (I3) of the present invention was used instead of R-1 as an emulsifying dispersant. Same sample as sample (A).

The same sample as sample (A) except that 1.0 g of exemplified compound (I5) was used as an emulsifying dispersant instead of R-1 of the present invention, and yellow of samples (A) to (F). Coupler (Y-1)
Instead, samples (G) to (L) and (M) to (R) were created using magenta coupler CM-1) and cyan coupler (C-1).

In addition, when using a magenta coupler, the coating amount of the coupler is 0.37 g/m, the silver coating amount of the silver chlorobromide emulsion consisting of 75 mol% Br is 0.20 g/m2, and the coating amount of the cyan coupler is 0.33 g/m2. m", and the wc coating amount of the silver chlorobromide emulsion consisting of 70 mo1% of Br was 0.28 g/m".

These samples were given a step exposure for sensitometry. Thereafter, experiments of treatments A and B were conducted using color developing solutions (A) and CB) as shown below.

The contents of treatments A and B are distinguished by the difference in the contents of color developing solutions (A) and (B), and the contents of other treatment steps are the same for both A and B.

(Processing process) (Temperature)
(Time) Developer: 38℃ 2.0 minutes Bleach-fix solution: 33℃
Washing with water for 1.5 minutes 28-35°C 3.0 minutes (Developer formulation) Color developer (A) Diethylenetriamine 5 vinegar i15 Na salt
2.0g benzyl alcohol
15ml diethylene glycol
10m1Naz soz
2. OgKB
r
o.5g hydroxylamine sulfate
3.0g4-amino-3-methyl-N-ethyl-N-[β-(methanesulfonamido)ethyl]
-p-phenylenediamine sulfate
5. OgNaz COz (I water salt)
30.0g fluorescent brightener (stilbene type) Add 1.0g water for a total volume of 1000ml
(I00O, 1) Color developer (B) Diethylenetriamine “acetic acid 5Na salt
2. OgNaz so3
2. OgKBr
Q, 5g hydroxylamine sulfate 3.0g 4-amino-3-methyl-N-ethyl-N-[β-(methanesulfonamido)ethyl]-p-phenylenediamine sulfate 5. OgNaz CO= (I water salt) 30.0g Fluorescent brightener (stilbene type > 1.0
Add water to make a total of 10 g
00ml (I00O, 1) (Bleach-fix solution formulation) Ammonium thiosulfate (54wt%)
150m1NazSOz
15gNHa (Fe (III)
(EDTA)) 55gEDT
A-2Na
Add 4g water to make the total amount,
1000ml100O, 9) Photographicity evaluation is based on maximum density (Dmax) and minimum density (D
This was done using two items: n+in). The results are shown in Table 1.

From the results in Table 1, it can be seen that regardless of whether yellow coupler, magenta coupler, or cyan coupler is used, the sample of the present invention has a higher maximum concentration than the comparative sample, and has almost the same color development as Treatment A even on a treatment day without benzyl alcohol. It can be seen that this shows that

Example 2 Comparative multilayer color photographic paper (A) having the layer structure shown in Table 2 was prepared on a paper support laminated on both sides with polyethylene.

The coating liquid was prepared as follows.

Daiichi Xu's Z, 11 Yellow coupler (a) 19.1g and color image stabilizer <b
27.2 ml of ethyl acetate and solvent (c
)7.9 mJ was added and dissolved, and this solution was used as an emulsifying dispersant to add 10% sodium dibutylnaphthalene sulfonate (R
-1) 12mI! 185ml of 10% gelatin aqueous solution containing
1 and emulsified and dispersed using a continuous VTA stirrer to obtain an emulsified dispersion.

On the other hand, silver chlorobromide emulsion (silver bromide 80 mol%, silver 70 g/
kg of gold containing silver chlorobromide and 1 kg of silver chlorobromide as shown below.
90gtJ was prepared as a blue sensitive layer emulsion with 7.0 x 10-' moles added per mole.

The emulsified dispersion and the emulsion were mixed and dissolved, and the gelatin concentration was adjusted to have the composition shown in Table 2 to prepare a first layer coating solution.

The coating solutions for the second to seventh layers were also prepared in the same manner as the first layer coating solution.

The gelatin hardening agent for each layer is 1-oxy-3゜5-
Dichloro-s-triazine sodium salt was used.

The following spectral sensitizers were used in each emulsion.

Blue-sensitive emulsion layer (7.OX 10-'m per mo1 silver halide
ol addition) (per 1 mo1 silver halide?, OX
10-'mol addition) (1 per mol of silver halide)
．． (addition of 10-' mol of OX) The following dyes were used as the eradication prevention dyes in each emulsion layer.

Green-sensitive emulsion layer: Red-sensitive emulsion 1i: The structural formulas of the compounds used in this example, such as couplers, are as follows.

(a) Yellow coupler (b) Color image stabilizer (e) Magenta coupler (f) Color image stabilizer (g) 2:1 mixture (weight ratio) of solvent H3 (h) 1:5 of 'R external radiation absorber :3 Mixture (molar ratio) (i) Color mixing prevention shoulder H H (D solvent (iso CqH + qO) TP=0 (k) Cyan coupler Cs
H+ r (t) (I) Ultraviolet absorber 0. ), Ya 1 “3:3?f
Item 6 (2) Tablet Next, photosensitive materials (B) to (D) were prepared as follows.

Once, in the 1st, 3rd and 5th layers of Kosha Danichi photosensitive material (A), 1 exemplified compound (I) of the present invention was added as an emulsifying dispersant instead of R-1.
．． Example of the present invention as an emulsifying dispersant in place of R-1 in the 1st, 3, and 5th layer of the photosensitive material (A), which is the same as the photosensitive material (A) except that 2 g is used. The same material as the photosensitive material (A) except that 1.2 g of compound (I1) was used. The same photosensitive material as photosensitive material (A) was used except that 1.2 g of the exemplary compound (I5) of the present invention was used as a dispersant.
WH type, color temperature of light source 3,200°K)
Gradation exposure for sensitometry was provided through green and red filters. The exposure at this time was carried out so that the exposure time was 0.5 seconds and the exposure amount was 250 CMS.

After this, use color developing solutions (A) and (B) as shown below.
Experiments for treatments A and B were conducted using the following.

The processing consisted of the steps of color development, bleach-fixing, and washing with water, and the photographic properties were evaluated by changing the development time to 1 minute, 2 minutes, and 3 minutes. The contents of treatments A and B represent the differences between the color developing solutions A and B, and the other treatment contents are the same for both A and B.

The evaluation of photographic properties is based on relative sensitivity, gradation, maximum density (Dma
x), minimum density (Dmin).

The relative sensitivity is a relative value with the sensitivity of each light-sensitive material taken as 100 when the color development time is 2 minutes in processing A of the light layer. Sensitivity was expressed as a relative value of the reciprocal of the exposure amount required to provide the minimum density plus 0.5. The gradation was expressed as the difference in density from the sensitivity point to the point where the logarithm of the exposure (gogE) increased by 0.5.

The results are shown in Table 3.

(1st season of processing (Warm Jf:)
(Time developer 38℃ 1.0~
3.0 minute bleach-fix solution 33℃
Wash with water for 1.5 minutes 28-35℃ 3.
0 minute α imager formulation) Color developer (A) Diethylenetriamine 5 vinegar b15Na salt
2.0g benzyl alcohol
15ml diethylene glycol
10m1N az SO'+
2. 0
g) (I3r
0. 5g hydroxylamine sulfate
3.0g4-amino-3-
Methyl-N-ethyl-N-[β-(methanesulfonamido)ethyl]-p-phenylenediamine sulfate5.
0g Na, Co, (l hydrate)
30.0g fluorescent brightener (stilbene type)
1. Add 0g water to total amount
1000ml Color developer (B) Diethylenetriamine 5 vinegar (I95N a salt
2.0gNazso:I
2. OgKBr
o, 5g hydroxylamine sulfate 3.0
g4-amino-3-methyl-N-ethyl-N-[β-(
methanesulfonamide) ethynolyp-phenylenediamine/sulfuric acid m s, og Na'z
CO3 (I water @ 30
．． 0g fluorescent brightener (stilbene type)
Add 1.0g water to total amount
1000ml (I00O, 1) (Bleach-fix solution formulation) Ammonium thiosulfate (54wt%)
150m1Naz soz
15gNHa (Fe (II)
I) (EDTA)) 55
gEDTA-2Na
Add 4g water to make the total amount
1000ml As is clear from Table 3, the photographic properties of the photosensitive materials (B) to (D) of the present invention in processing B are smaller in relative sensitivity, gradation, and maximum density compared to the comparative photosensitive material (A). It can be seen that treatment B, which does not contain benzyl alcohol, also exhibits performance comparable to treatment A.

Furthermore, the light-sensitive materials (B) to (D) of the present invention exhibited good photographic properties even on processing days that did not contain benzyl alcohol, with a development time of 2 minutes.

(Effects of the present invention) By implementing the present invention, benzyl alcohol is substantially eliminated, reducing the pollution load and reducing liquid preparation work.
It has the effect of eliminating the decrease in density caused by cyan dye remaining as a leuco body. Further, by using the silver halide emulsion of the present invention, it is possible to obtain photographic properties with high Dmax, low Dmin, and little change in sensitivity and gradation even if benzyl alcohol is eliminated.

1. Display of incident 1985 Patent Application No. 18485 2. Name of the invention Color image forming method 3. Person making the amendment 4. I＼J锂P人

Claims (1)

[Scope of Claims] A silver halide color photographic material having a photographic layer containing a compound represented by the general formula (I) provided on a reflective support is subjected to color development substantially free of benzyl alcohol after exposure. 1. A color image forming method characterized by developing with a liquid in a time of 2 minutes and 30 seconds or less. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 represents a substituted or unsubstituted alkyl group or aromatic group, and R_2 is a hydrogen atom or ▲There are mathematical formulas, chemical formulas, tables, etc. ▼ (here, L_4 represents a divalent linking group, R_5 represents a hydrogen atom or a substituted or unsubstituted alkyl or aromatic group), and R_3 and R_4
independently represents a hydrogen atom or a substituted or unsubstituted alkyl group. L_1 represents a divalent linking group, and L_2 and L_3 each independently represent a single bond or a divalent or trivalent linking group. n represents an integer of 1 or 2. A represents a repeating unit copolymerized with an ethylenically unsaturated monomer copolymerizable with the monomer providing the y component and the z component. X_1 and X_2 each independently represent a hydrogen atom or cation, and x, y, and z each represent a value indicating the average number of moles added of each monomer. Q represents a monovalent group. ]